Opdigte reaktive overflader med børste-agtig og Crosslinked film af Azlactone-Functionalized blok Co polymerer
Summary
Overflade fabrikation metoder for mønstrede aflejring af nanometer tyk pensler eller mikron tyk, crosslinked film af en azlactone blok Co-polymer er rapporteret. Kritiske eksperimenterende trin, repræsentative resultater og begrænsninger af hver metode diskuteres. Disse metoder er nyttige til at skabe funktionelle grænseflader med skræddersyede fysiske funktioner og afstemmelige overflade reaktivitet.
Abstract
I dette papir, fabrikation metoder, der genererer nye overflader ved hjælp af azlactone-baseret blok Co-polymer, poly (glycidyl methylmethacrylat) –blok– poly (vinyl dimethyl azlactone) (PGMA –b– PVDMA), præsenteres. Høj reaktivitet af azlactone grupper mod Amin, thiol og hydroxylgrupper, kan PGMA –b– PVDMA overflader ændres med sekundære molekyler til at skabe kemisk eller biologisk functionalized grænseflader til en lang række applikationer. Tidligere rapporter af mønstrede PGMA –b– PVDMA grænseflader har brugt traditionel topstyret mønstre teknikker, der genererer uensartet film og dårligt kontrolleret baggrund kemi. Her beskriver vi tilpassede mønstre teknikker, der gør det muligt præcist deposition af meget ensartet PGMA –b– PVDMA film i baggrunde, der er kemisk inert, eller som har biomolekyle-frastødende egenskaber. Vigtigere, er disse metoder designet til indbetaling PGMA –b– PVDMA film på en måde, der helt bevarer azlactone funktionalitet gennem hver behandlingstrin. Mønstrede film Vis velkontrollerede tykkelser, der svarer til polymer pensler (~ 90 nm) eller stærkt krydsbundet strukturer (~ 1-10 μm). Penselmønstre genereres ved hjælp af enten parylene lift-off eller grænseflade instrueret forsamling metoder beskrevet og er nyttige for præcise graduering af samlede kemiske overflade reaktivitet ved at justere enten PGMA –b– PVDMA mønster tætheden eller den længde af VDMA blok. Derimod tykt crosslinked PGMA –b– PVDMA mønstre er opnået ved hjælp af et tilpassede mikro-kontakt teknik og tilbyder fordel for højere lastning eller erobringen af sekundært materiale på grund af højere areal til volumen nøgletal. Detaljerede eksperimenterende trin, kritiske film beskrivelser og fejlfinding guider for hver fabrikationsanlæg metode diskuteres.
Introduction
Udvikle fabrication teknikker, der giver mulighed for alsidig og præcis kontrol af kemiske og biologiske overflade funktionalitet er ønskeligt for en lang række applikationer, fra erobringen af miljøforurenende til udvikling af næste generation biosensorer, implantater og tissue engineering enheder1,2. Funktionelle polymerer er fremragende materialer til tuning overfladeegenskaber gennem “podning fra” eller “podning til” teknikker3. Disse tilgange giver mulighed for kontrol af overflade reaktivitet baseret på monomeren kemisk funktionalitet og molekylvægt af polymer4,5,6. Azlactone-baserede polymerer er blevet intenst undersøgt i denne forbindelse som azlactone grupper hurtigt par med forskellige nukleofiler i ring-åbning reaktioner. Dette omfatter primær aminer, alkoholer, dithioler og hydrazin grupper, hvilket giver en alsidig rute for yderligere overflade functionalization7,8. Azlactone-baserede polymer film har været ansat i forskellige miljømæssige og biologisk programmer herunder analysand fange9,10, celle kultur6,11, og groedehindrende / anti-klæbende belægninger12. I mange biologiske programmer er mønster azlactone polymer film på nano til mikrometer længdeskalaer ønskeligt at lette fysisk kontrol af biomolekyle præsentation, cellulære vekselvirkninger, eller til at modulere overflade interaktioner13, 14,15,16,17,18. Fabrikation metoder bør derfor udvikles for at tilbyde høj mønster ensartethed og velkontrollerede filmtykkelse, uden at kompromittere kemisk funktionalitet19.
For nylig, Lokitz et al. udviklet en PGMA –b– PVDMA blokcopolymer som var i stand til at manipulere overflade reaktivitet. PGMA blokke par oxid-bærende overflader, hvilket giver høj og afstemmelige overflade tætheder af azlactone grupper20. Tidligere anvendes rapporteret metoder til mønster denne polymer for oprettelsen af biofunctional grænseflader traditionelle top-down fotolitografi tilgange, der genererede uensartet polymer film med baggrunden områder forurenet med resterende photoresist materiale, hvilket medfører høje niveauer af ikke-specifikke kemiske og biologiske vekselvirkninger21,22,23. Her, forårsaget forsøg på at passivering baggrund regioner krydsreaktion med azlactone grupper, at kompromittere polymer reaktivitet. I betragtning af disse begrænsninger, vi for nylig udviklet teknikker til mønster børste (~ 90 nm) eller stærkt krydsbundet (~ 1-10 μm) film af PGMA –b– PVDMA til kemisk eller biologisk inaktivt baggrunde på en måde, der helt bevarer kemiske funktionaliteten af polymer24. Disse præsenterede metoder udnytte parylene lift-off, interface-instrueret Forsamling (IDA) og brugerdefinerede microcontact (μCP) trykteknikker. Meget detaljerede eksperimentelle metoder for disse mønstre tilgange, samt kritisk film beskrivelser og udfordringer og begrænsninger i forbindelse med hver teknik præsenteres her i skriftlig og video format.
Protocol
Representative Results
Discussion
Denne artikel præsenterer tre tilgange til mønster PGMA –b– PVDMA, hver med sit sæt af fordele og ulemper. Metoden parylene lift-off er en alsidig metode til mønster block Co polymerer på micro nanoskala resolution, og har været brugt som en aflejring maske i andre mønstre systemer33,34,35. På grund af sin relativt svage overflade vedhæftning, kan parylene stencil let fjernes fra overfladen ved hjælp af sonike…
Disclosures
The authors have nothing to disclose.
Acknowledgements
Denne forskning blev støttet af Kansas State University. En del af denne forskning blev udført på Center for Nanophase materialer videnskaber, der er sponsoreret på Oak Ridge National Laboratory af videnskabelige bruger faciliteter Division, Office of grundlæggende energi Sciences og US Department of Energy.
Materials
| Material | |||
| Ethanol, ≥ 99.5% | Sigma-Aldrich | 459844 | – |
| HCL, 1.019 N in H2O | Fluka Analytical | 318949 | – |
| Acetone, ≥ 99.5% | Sigma-Aldrich | 320110 | – |
| Benzene, ≥ 99.9% | Sigma-Aldrich | 270709 | – |
| Isopropanol, ACS reagent, ≥99.5% | Sigma-Aldrich | 190764 | |
| Hexane | Fisher Chemical | H292-4 | – |
| Argon | Matheson Gas | G1901175 | – |
| Tetrahydrofuran (THF), ≥ 99.9% | Sigma-Aldrich | 401757 | – |
| Pluronic F-127 | Sigma-Aldrich | P2443 | – |
| Polydimethyl Siloxane (PDMS) Slygard 184 | Dow Corning | 4019862 | – |
| Trichloro (1H,1H,2H,2H-perfluorooctyl) silane (TPS), 97% | Sigma-Aldrich | 448931 | It is toxic. Work with it under hood |
| Anhydrous Chloroform, ≥ 99% | Sigma-Aldrich | 372978 | – |
| Positive Photoresist AZ1512 | MicroChemicals | AZ 1512 | amber-red liquid, density 1.083 g/cm3, spin coating step should be done under the hood |
| Developer AZ 300 MIF | MicroChemicals | AZ300 MIF | clear colourless liquid with slight amine odor and density of 1 g/cm3 |
| 1,2-Vinyl-4,4- dimethyl azlactone (VDMA) | Isochem North America, LLC | VDMA | – |
| 2-cyano-2-propyl dodecyl trithiocarbonate (CPDT) | Sigma-Aldrich | 723037 | – |
| 2,2′-Azobis (4methoxy-2,4-dimethyl valeronitrile) (V-70) | Wako Specialty Chemicals | CAS NO. 15545-97-8, EINECS No. 239-593-8 | – |
| Parylene N | Specialty Coating Systems | 15B10004 | – |
| Name | Company | Catalog Number | Comments |
| Equipment | |||
| Parylene Coater | Specialty Coating Systems | SCS Labcoater (PDS 2010) | – |
| Mask alignment system | Neutronix Quintel | NXQ8000 | – |
| Oxygen Plasma Etcher | Oxford Instruments | Plasma Lab System 100 | – |
| Surface Profilometer | Veeco | Dektak 150 | Scan type was standard hill. Scan duration and force were 120 s and 1 mg, respectively. |
| Brightfield Upright Microscope | Olympus Corporation | BX51 | – |
| Oxygen Plasma Cleaner | Harrick Plasma | PDC-001-HP | – |
| Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) | Perkin Elmer | ATR-FTIR 100 | – |
| Atomic Force Microscopy (AFM) | PicoPlus | Picoplus atomic force microscope | Veeco MLCT-E cantilevers with a 0.5 N/m spring constant. Scan speeds varied between 0.25 and 1 Hz. |
| Scanning Electron Microscopy (SEM) | Hitachi Science Systems Ltd., Tokyo, Japan | – | – |
| Rotary Tool Workstation | Dremel | Model 220-01 | – |
| Spin Coater | Smart Coater | SC100 | – |
| Vacuum Oven | Yamato Scientific Co. | PCD-C6(5)000) | – |
| Size Exclusion Chromatography (SEC) | Waters Alliance 2695 Separations Module | 720004547EN | – |
| Refractive Index (RI) detector | Waters | Model 2414 | – |
| Photodiode Array Detector | Waters | Model 2996, 716001286 | – |
| Multi-angle Light Scattering (MALS) Detector | Wyatt Technology | miniDAWN TREOS II | – |
| Viscometer | Wyatt Technology | Viscostar | – |
| PLgel 5 µm mixed-C columns (300 x 7.5 mm) | Agilent | 5 µm mixed-C columns | – |
| Ellipsometer | J. A. Woollam | alpha-SE | Cauchy model, PGMA and PVDMA layers had refractive indices of 1.50 and 1.52 at 632 nm |
| Ultrasonic Sonicator | Fischer Scientific | FS-110H | – |
References
- Faia-Torres, A., Goren, T., Textor, M., Pla-Roca, M. Patterned Biointerfaces. Comprehensive biomaterials. , 181-201 (2017).
- Ogaki, R., Alexander, M., Kingshott, P. Chemical patterning in biointerface science. Materials Today. 13 (4), 22-35 (2010).
- Rungta, A., et al. Grafting bimodal polymer brushes on nanoparticles using controlled radical polymerization. Macromolecules. 45 (23), 9303-9311 (2012).
- Guyomard, A., Fournier, D., Pascual, S., Fontaine, L., Bardeau, J. Preparation and characterization of azlactone functionalized polymer supports and their application as scavengers. European Polymer Journal. 40 (10), 2343-2348 (2004).
- Zayas-Gonzalez, Y. M., Lynn, D. M. Degradable Amine-Reactive Coatings Fabricated by the Covalent Layer-by-Layer Assembly of Poly (2-vinyl-4, 4-dimethylazlactone) with Degradable Polyamine Building Blocks. Biomacromolecules. 17 (9), 3067-3075 (2016).
- Schmitt, S. K., et al. Peptide Conjugation to a Polymer Coating via Native Chemical Ligation of Azlactones for Cell Culture. Biomacromolecules. 17 (3), 1040-1047 (2016).
- Yu, Q., Cho, J., Shivapooja, P., Ista, L. K., López, G. P. Nanopatterned smart polymer surfaces for controlled attachment, killing, and release of bacteria. ACS Applied Materials & Interfaces. 5 (19), 9295-9304 (2013).
- Jones, M. W., Richards, S., Haddleton, D. M., Gibson, M. I. Poly (azlactone)s: versatile scaffolds for tandem post-polymerisation modification and glycopolymer synthesis. Pilymer Chemistry UK. 4 (3), 717-723 (2013).
- Barkakaty, B., et al. Amidine-Functionalized Poly (2-vinyl-4, 4-dimethylazlactone) for Selective and Efficient CO2 Fixing. Macromolecules. 49 (5), (2016).
- Cullen, S. P., Mandel, I. C., Gopalan, P. Surface-anchored poly (2-vinyl-4, 4-dimethyl azlactone) brushes as templates for enzyme immobilization. Langmuir. 24 (23), 13701-13709 (2008).
- Schmitt, S. K., et al. Polyethylene glycol coatings on plastic substrates for chemically defined stem cell culture. Advanced Healthcare Materials. 4 (10), 1555-1564 (2015).
- Yan, S., et al. Nonleaching Bacteria-Responsive Antibacterial Surface Based on a Unique Hierarchical Architecture. ACS Applied Materials & Interfaces. 8 (37), 24471-24481 (2016).
- Li, C., et al. Creating "living" polymer surfaces to pattern biomolecules and cells on common plastics. Biomacromolecules. 14 (5), 1278-1286 (2013).
- Brétagnol, F., et al. Surface functionalization and patterning techniques to design interfaces for biomedical and biosensor applications. Plasma Processes and Polymers. (6-7), 443-455 (2006).
- Thery, M. Micropatterning as a tool to decipher cell morphogenesis and functions. Journal of Cell Science. 123 (Pt 24), 4201-4213 (2010).
- Robertus, J., Browne, W. R., Feringa, B. L. Dynamic control over cell adhesive properties using molecular-based surface engineering strategies. Chemical Soceity Reviews. 39 (1), 354-378 (2010).
- Kane, R. S., Takayama, S., Ostuni, E., Ingber, D. E., Whitesides, G. M. Patterning proteins and cells using soft lithography. Biomaterials. 20 (23), 2363-2376 (1999).
- Cattani-Scholz, A., et al. PNA-PEG modified silicon platforms as functional bio-interfaces for applications in DNA microarrays and biosensors. Biomacromolecules. 10 (3), 489-496 (2009).
- Nie, Z., Kumacheva, E. Patterning surfaces with functional polymers. Nature Materials. 7 (4), (2008).
- Lokitz, B. S., et al. Manipulating interfaces through surface confinement of poly (glycidyl methacrylate)-block-poly (vinyldimethylazlactone), a dually reactive block copolymer. Macromolecules. 45 (16), 6438-6449 (2012).
- Kratochvil, M. J., Carter, M. C., Lynn, D. M. Amine-Reactive Azlactone-Containing Nanofibers for the Immobilization and Patterning of New Functionality on Nanofiber-Based Scaffolds. ACS Applied Materials & Interfaces. 9 (11), 10243-10253 (2017).
- Wancura, M. M., et al. Fabrication, chemical modification, and topographical patterning of reactive gels assembled from azlactone-functionalized polymers and a diamine. Journal of Polymer Science Part A1. 55 (19), 3185-3194 (2017).
- Hansen, R. R., et al. Lectin-functionalized poly (glycidyl methacrylate)-block-poly (vinyldimethyl azlactone) surface scaffolds for high avidity microbial capture. Biomacromolecules. 14 (10), 3742-3748 (2013).
- Masigol, M., Barua, N., Retterer, S. T., Lokitz, B. S., Hansen, R. R. Chemical copatterning strategies using azlactone-based block copolymers. Journal of Vacuum Science and TechnologyB. 35 (6), 06GJ01 (2017).
- Lokitz, B. S., et al. Dilute solution properties and surface attachment of RAFT polymerized 2-vinyl-4, 4-dimethyl azlactone (VDMA). Macromolecules. 42 (22), 9018-9026 (2009).
- Aden, B., et al. Assessing Chemical Transformation of Reactive, Interfacial Thin Films Made of End-Tethered Poly (2-vinyl-4, 4-dimethyl azlactone)(PVDMA) Chains. Macromolecules. 50 (2), 618-630 (2017).
- Hansen, R. H., et al. Stochastic assembly of bacteria in microwell arrays reveals the importance of confinement in community development. Public Library of Science One. 11 (5), e0155080 (2016).
- Vargis, E., Peterson, C. B., Morrell-Falvey, J. L., Retterer, S. T., Collier, C. P. The effect of retinal pigment epithelial cell patch size on growth factor expression. Biomaterials. 35 (13), 3999-4004 (2014).
- Tzvetkova-Chevolleau, T., et al. Microscale adhesion patterns for the precise localization of amoeba. Microelectronic Engineering. 86 (4), 1485-1487 (2009).
- Shelly, M., Lee, S., Suarato, G., Meng, Y., Pautot, S. Photolithography-Based Substrate Microfabrication for Patterning Semaphorin 3A to Study Neuronal Development. Semaphorin Signaling: Methods and Protocols. 1493, 321-343 (2017).
- McDonald, J. C., et al. Fabrication of microfluidic systems in poly(dimethylsiloxane). Electrophoresis. 21 (1), 27-40 (2000).
- Hansen, R. R., et al. High content evaluation of shear dependent platelet function in a microfluidic flow assay. Annals of Biomedical Engineering. 41 (2), 250-262 (2013).
- Segalman, R. A., Yokoyama, H., Kramer, E. J. Graphoepitaxy of spherical domain block copolymer films. Advanced Materials. 13 (15), 1152-1155 (2001).
- Stoykovich, M. P., et al. Directed assembly of block copolymer blends into nonregular device-oriented structures. Science. 308 (5727), 1442-1446 (2005).
- Craig, G. S., Nealey, P. F. Self-assembly of block copolymers on lithographically defined nanopatterned substrates. Journal of Polymer Science and Technology. 20 (4), 511-517 (2007).
- Kodadek, T. Protein microarrays: prospects and problems. Chemical Biology. 8 (2), 105-115 (2001).
- Atsuta, K., Suzuki, H., Takeuchi, S. A parylene lift-off process with microfluidic channels for selective protein patterning. Journal of Micromechanics and Microengineering. 17 (3), 496 (2007).
- Ramanathan, M., Lokitz, B. S., Messman, J. M., Stafford, C. M., Kilbey, S. M. Spontaneous wrinkling in azlactone-based functional polymer thin films in 2D and 3D geometries for guided nanopatterning. Journal of Material Chemistry C. 1 (11), 2097-2101 (2013).
- Suh, K. Y., Jon, S. Control over wettability of polyethylene glycol surfaces using capillary lithography. Langmuir. 21 (15), 6836-6841 (2005).
- Buck, M. E., Lynn, D. M. Layer-by-Layer Fabrication of Covalently Crosslinked and Reactive Polymer Multilayers Using Azlactone-Functionalized Copolymers: A Platform for the Design of Functional Biointerfaces. Advanced Engineering Materials. 13 (10), 343-352 (2011).
- Ma, L., et al. Trap Effect of Three-Dimensional Fibers Network for High Efficient Cancer-Cell Capture. Advanced Healthcare Materials. 4 (6), 838-843 (2015).
- Massad-Ivanir, N., Shtenberg, G., Tzur, A., Krepker, M. A., Segal, E. Engineering nanostructured porous SiO2 surfaces for bacteria detection via "direct cell capture". Analytical Chemistry. 83 (9), 3282-3289 (2011).
- Ilic, B., Craighead, H. Topographical patterning of chemically sensitive biological materials using a polymer-based dry lift off. Biomedical Microdevices. 2 (4), 317-322 (2000).
- Gates, B. D., et al. New approaches to nanofabrication: molding, printing, and other techniques. Chemical Reviews. 105 (4), 1171-1196 (2005).
- Jonas, U., del Campo, A., Kruger, C., Glasser, G., Boos, D. Colloidal assemblies on patterned silane layers. Proceedings of the National Academy of Sciences USA. 99 (8), 5034-5039 (2002).
- Qin, D., Xia, Y., Whitesides, G. M. Soft lithography for micro-and nanoscale patterning. Nature Protocols. 5 (3), 491-502 (2010).
